HU185902B - Herbicides containing substituted n-benzoyl-anthranilic acid derivatives and anhydro-compounds thereof and process for preparing the active substances - Google Patents

Description

The present invention relates to herbicides containing substituted N-benzoyl anthranilic acid derivatives and their anhydro compounds as well as a process for the preparation of substituted N-benzoyl anthranilic acid derivatives and their anhydro compounds.

Nbenzoyl anthranilic acid derivatives and their anhydro compounds as well as benzoyl-substituted derivatives of N-benzoyl anthranilic acid and their anhydro compounds are known from German Patent No. 1,191,171 and French Patent No. 1,373,264. The results of the Examples described in the specification show that a very limited number of weeds can be controlled at relatively high doses of unsubstituted N-benzoylanthranilic acid and its anhydro compound. The active ingredients. monocotyledonous and dicotyledonous crops are well tolerated.

Numerous substituted anhydro compounds, i.e. 4-substituted 3-phenyl-benzoxazin-4-one containing a 2-substituted phenyl group, are disclosed in U.S. Patent Nos. 3,914,121 and 3,970,652 as non-phytotoxic and suitable herbicides. Because of their high dose required for their action, they are worthless herbicides.

U.S. Patent Nos. 3,914,121 and 3,970,652 emphasize 2-aryl-4H-3,1-benzoxazin-4-one derivatives such as 2- (m-trifluoromethylphenyl) -4H-3,1-benzoxazine. 4-especially beneficial herbicides in cereals and broadleaf weeds in soy. It is striking that the dose applied is extremely high - 11 kg per hectare. Although numerous monocotyledonous and dicotyledonous plants have been mentioned to demonstrate the phytotoxicity of the active compounds, there is no mention of the characteristic representatives of broad-leaved weeds in arable land.

It has been found that herbicides containing the substituted N-benzoyl anthranilic acid derivatives of formula (1) and their anhydrous compounds of formula (II) as active ingredients have a relatively small amount of selective herbicidal activity.

In the formulas (I) and (II), R ¹ is a phenyl of the formula (a) or (b); in these groups one of R ³ and R ^{4 represents a} halogen atom, a nitro group or a C 1 -C 4 haloalkyl group and the other represents a hydrogen or halogen atom; R ¹ further 6-chloro-3-pyridazinyl,

Furthermore R ¹ represents 6-chloro-3-pyridazinyl, 3-bromo-6-pyridyl, or 3-nitro-6-pyridyl;

R ^{2 is} hydrogen or nitro,

X is hydrogen or halogen, C1-C4 alkyl or C1-C4 alkoxy, and

Y is OR ⁶ or -;

in these groups R ^{e is a} hydrogen atom, an alkali metal cation or a C 1-4 alkyl group, or

R ^{1 is} hydrogen or C 1-4 alkyl and R ^{8 is C} 1-4 alkyl. In formula (I) or the general ⁵ formula (II): R * is thus (a) or (b) a substituted phenyl group of the formula; in these groups, R ³ and R * are, for example, hydrogen, fluorine, chlorine, bromine or iodine, nitro, trifluoromethyl, difluoromethyl, difluorochloromethyl, 1-chloroethyl, 2- chloroethyl, 1 ^0-fluoro ethyl, 2-fluoroethyl ·, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl -, l, l, 2-trifluoro-2-klóresil-, 1,1,2,2,2-pentafluoroethyl group, or ^R1 6-chloro-3-pyridazinyl, 3-bromo-6-pyridyl, 3-nitro-6-pyridinyl group.

^5. R ² is hydrogen or nitro. X may be, for example, hydrogen, fluorine, chlorine, bromine or iodine, methyl, ethyl, η-propyl, 2-propyl, n-butyl, tert-butyl, methoxy, ethoxy.

> 0 Y is a group of the formula -O-R ⁶ or -G, and in these groups R ^{6 is,} for example, hydrogen, methyl, ethyl, η-propyl, isopropyl, η-butyl, sec-butyl, isobutyl, tert-butyl, lithium, potassium, sodium ion, and ²⁵ atoms, methyl, ethyl, η-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or ^R7 and ^R8 represent hydrogen .

Preferred compounds of formula I or II are those in which R ^{1 is} phenyl, R ^{2 is} hydrogen or nitro, R ^{1 is} substituted by halogen and / or haloalkyl, in particular ³⁰ chlorine and trifluoromethyl, X is hydrogen. or a halogen atom, a C 1 -C 4 alkyl or alkoxy group, in particular a hydrogen atom, a chlorine atom, a methyl group ³⁵ or a methoxy group, and Y in the case of compounds of formula I - OR ⁶ and R ⁶ hydrogen atom; Represents a C4-alkyl group, in particular a methyl group or an alkali metal cation.

According to the present invention, the Nbenzoyl anthranilic acid derivatives of formula I are prepared by providing an anthranilic acid derivative of formula III, wherein X and Y are as defined above, in an approximately stoichiometric amount of substituted benzoyl of formula IV halide, wherein R 1 and R ^{2 are} as defined above and Hal is halogen, in particular fluorine, chlorine or bromine, in an aqueous-basic medium or optionally in the presence of an acid scavenger Ό in an inert organic solvent, at a temperature between 30 ° C and 150 ° C.

When anthranilic acid and 3- (3'-chloro-4 '- (trifluoromethyl) -phenoxy) -benzoic acid chloride are used as starting materials, the reaction is illustrated in Scheme [A].

The anthranilic acid derivative (III) is conveniently reacted in an aqueous-alkaline medium with about an equivalent amount of the benzoyl halide (IV) and at least an equivalent amount of alkali metal hydroxide relative to each of the starting materials [J. Org. Chem. 9, 396-400 (1944)]. The reaction may optionally be carried out in the presence of an acid scavenger and an inert organic solvent. Both change of procedure-21. In the prior art, the operating temperature may range from -30 ° C to +150 ° C, preferably from + 20 ° C to + 80 ° C.

The reaction may also be carried out in continuous or batch mode.

The inert organic solvents used in the process of the invention are hydrocarbons such as ligroin, benzene, toluene, pentane, hexane, cyclohexane, petroleum ether; aliphatic and aromatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,1- and 1,2-dichloroethane, 1,1,1- and

1,1,2-trichloroethane, chlorobenzene, ο-, m- or p-dichlorobenzene, ο-, m- or chlorotoluene; aliphatic and aromatic nitrocarbons such as nitrobenzene, nitroethane, ο-, m- or p-nitrotoluene; a nitrile such as acetonitrile, isobutyronitrile, butyronitrile; an ether such as diethyl ether, di-n-propyl ether, tetrahydrofuran, dioxane; an ester such as acetic acetate, ethyl acetate or isobutyl acetate; amide such as formamide, methylformamide and dimethylformamide and the like. can be used.

Suitable acid scavengers are, for example, alkali metal hydroxide, alkali metal carbonate and a tertiary organic base. Particularly suitable are sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, pyridine, trimethylamine, α-, β- and γ-picoline, lutidine, Ν, Ν-dimethylaniline, N, N-dimethylcyclohexylamine, quinoline , tri-n-propylamine, tri-n-butylamine, acridine.

The starting compounds of formulas (III) and (IV) may be administered in any order.

After completion of the reaction, the product of formula I can be isolated from the reaction mixture by filtration of the precipitate. When the final product is soluble in a solvent, the solvent is removed under reduced pressure, the residue is dissolved in an alkali metal hydroxide solution, filtered and acid is added. The product was isolated by filtration and the resulting residue was recrystallized or chromatographed. If the desired N-benzoyl anthranilic acid derivative is in the precipitate, it is mixed with water and filtered again.

The anhydro compounds of formula II can be prepared by reacting an anthranilic acid derivative of formula V, wherein X is as defined above, and a benzoyl halide of formula IV, wherein R ¹ and R ² said halogen atom, in particular fluorine, chlorine or bromine, in the presence of an aromatic tertiary amine in the presence of 0 to 150 ° C.

If anthranilic acid and double the amount

The reaction of 3- (3'-chloro-4 '- (trifluoromethyl) -phenoxy) -benzoic acid chloride in the presence of pyridine as a tertiary aromatic amine is illustrated in Scheme [B].

Aromatic tertiary amines useful in the process include pyridine, quinoline, α-, β- or γ-picoline, acridine, α- and γ-lutidine. The amount of amine used is 2 to 10 times per mole of anthranilic acid derivative of formula (V).

This operation is conveniently carried out by adding the benzoyl halide to a solution of the anthranilic acid derivative in the amine. The operation can be performed continuously or intermittently. The reaction temperature may be between 0 and 150 'C, preferably between 20 and 80' C. [J. Chem. Soc.

(c) 1968, 1593-1597],

The compounds of formula (II) may be isolated by stirring the reaction mixture with water. ⁵ the residue is filtered off, optionally traces of acidic impurities removed by alkali washing, and then purified by recrystallization or chromatography.

The anhydro general formula (II) is prepared at ¹⁰ by cyclization of layouts can be carried out between 0 and 150 ° C in the presence of (I) is reacted with N-benzoyl-anthranilic acid derivative with a dehydrating agent.

Insofar as the production of anhidrovegyület using N- presence of a dehydrating agent - using [3- (3'-chloro-4 '/ ¹⁵ trifluoromethyl / -phenoxy) benzoyl] anthranilic acid is carried out, then the reaction shown in the reaction scheme [C] takes place.

The method of dehydrating agent is a carboxylic acid anhydride such as acetic anhydride, propionic anhydride ^20, butyric anhydride; mixed carboxylic acid anhydride such as formic-acetic anhydride, formic acid, propionic anhydride, hangyasavvajsav anhydride, acetic acid anhydride, acetic acid anhydride, propionic acid ²⁵ anhydride, and dicyclohexylcarbodiimide and thionyl chloride can be used. The ring closure is carried out in the presence of from 1 to 10 moles of water scavenger based on the amount of the N-benzoyl anthranilic acid derivative of formula (I).

³⁰ · The process is between 0 and 150 ° C, preferably 50 to

At 100 ° C, it can be carried out continuously or intermittently for 0.5 to 5 hours.

The reaction mixture is concentrated to dryness to isolate the final product. Optionally, the resulting residue may be freed from traces of acidic contamination by alkaline washing in ³⁵ and then purified by recrystallization or chromatography [J. Org. Chem.

967-981 (1949)].

The benzoyl halides of general formula (IV) used as starting materials may be prepared from the corresponding benzoic acid derivatives in a known manner (Houben-Weyl, Methoden der. Organ. Chem.

Volume 8, page 463; Georg Thieme-Verlag, Stuttgart, 1952). Substituted benzoic acid derivatives of phenoxy and heteroaryloxy45 are, according to Williamson ether synthesis, prepared from the corresponding phenolate of 3-hydroxybenzoic acid and the corresponding halobenzene.

The following Examples illustrate the preparation of compounds of Formulas I and II50. The volume parts are proportional to the parts by weight as liters per kg.

Example 1

N- [3 '- (2-Chloro-4- (trifluoromethyl) -phenoxy) -6'-nitrobenzoyl] -thranilic acid methyl ester

75.58 sr. anthranilic acid methyl ester 500 vol. To a solution of Part 60 in anhydrous diethyl ether was added dropwise at room temperature 190 ml. Part 3- (2'-chloro-4 '- (trifluoromethyl) phenoxy) -6-nitrobenzoic acid chloride 120 vol. of anhydrous diethyl ether and 50.5 parts by weight. triethylamine. Then, the reaction mixture being heated to reflux for _65,

After stirring for 185 hours, cool and suction. The resulting residue was stirred at 2000 sr. water, then suction. 240 sr. (9796) to give the title compound; m.p. 123-126 ° C.

Example 2. N- [3 '~ (2' -chloro-4- (trifluoromethyl) -phenoxy) -6'-nitrobenzoyl] -anthranilic acid

247 sr. N- [3 '- (2-Chloro- ^4'Z- (trifluoromethyl-phenoxy) -6'-nitrobenzoyl] -anthranilic acid methyl ester 33.7 sr. potassium hydroxide 200 sr. water and 200 vol. of ethanol was heated under reflux for 1 hour. The reaction mixture was cooled and the clear solution was acidified with 3N hydrochloric acid. An oil precipitates out and is taken up in diethyl ether. Addition of petroleum ether gives a crystalline product; aspirated 200 sr. Yield (83%); mp 187-192 ° C.

Example 3

N- [3'- (2-Chloro-4- (trifluoromethyl) -phenoxy) -6'-nitrobenzoyl] -an tranyl acid

6.9 sr. to a solution of anthranilic acid in 100 volumes of anhydrous tetrahydrofuran at room temperature was added dropwise dropwise to 18.1 sr. A solution of 3- (2'-chloro-4 '- (trifluoromethyl) -phenoxy) -6-nitrobenzoic acid chloride in 40 volumes of anhydrous tetrahydrofuran; triethylamine. The reaction mixture was then heated to reflux and stirred for one hour. After cooling, the reaction mixture is filtered off with suction and the filtrate is evaporated. The oily residue was dissolved in 40 volumes of diethyl ether, extracted once with dilute hydrochloric acid and twice with brine. The combined alkaline phase was acidified with 2N hydrochloric acid and the product was filtered off with suction. Ten sr. Yield (42%); mp 182-185 ° C.

EXAMPLE 4 Sodium ^N- [d '- (2-Chloro-4-trifluoromethyl-phenoxy) -6'-nitrobenzoyl] -anthranilic acid, m.p. N- [3 '- (2-chloro-4- (trifluoromethyl) phenoxy) -6-nitrobenzoyl] anthranilic acid is added in 2 sr. sodium hydroxide in 100 volumes of anhydrous methanol and stirred for 1 hour at room temperature. After evaporation of the solution, 25 ml of the residue remain. (100%) of the title sodium salt was obtained.

Elemental Composition (%): Calculated: C 50.2 H 2.2 N 5.6 Cl 7.1 Na 4.8 Found: C 49.9 H 2.6 N 5.6 Cl 7.0 Na 4 0

Example 5

2- [3 '- (2-Chloro-4- (trifluoromethyl-phenoxy) -6'-nitrophenyl] -4H-1,3-benzoxazin-4-one m.p. N- [3- (2'-chloro-4 '- (trifluoromethyl) -phenoxy) -6-nitrobenzoyl] -thranilic acid 200 µl. with acetic anhydride and refluxed for 4 hours. The reaction mixture was then filtered and the filtrate evaporated in vacuo. The residue was recrystallized from ethanol with 18 sr. Yield: 78%; 131-135 ° C.

In a manner analogous to that described in the previous examples, the compounds of formula (I) in Table I and the compound of formula (II) may be prepared. Table II.

Table I

Row song R ¹ R ² X Y Melting point, ° C 15 6th phenyl H H OH 7th phenyl from ₂ H OH 8th 4-chlorophenyl H H OH 9th 4-chlorophenyl from ₂ H OH 20 op. R ° c] number Irish R * X Y cl -io · - / ^ - Cl H H OH 25 cl 1 from ₂ H OH 125-150 cl • 12 H H OH 30 cl • 13 . B- \ H ° ₂ H OH 35 111 H H OH 15 P from ₂ H OH 40 15 cl H H OH cl 45 17 -Mci Cl ' from ₂ H OH 18 H H OH 50 F 19 K ° ₂ H OH 55 20 cl H H OH 178-183 21 H H OCHj. .88-92 60 cl 22 M ^CP 3 ci H H OH

185,902

Sofaiém ^r1 R ² X Y M.p. Sp | -enen ft ¹ F ² X Y op. [ _0l 2J Cl j £> ^cp 5 Cl> ^ Nog H 'OH 47 N0 ₂ 3-F OH 24 - @ - « ⁰ 2 H H OCH 125-127 48 - ^> ^CP 3 ho ₂ H OCH 169-172 25 - © - * 2 ° H H OH 204-206 49 ^ ^p 3 KO ₂ H OH 181-185 26 © 2 >> cl H H OH 197-201 50 H 4-C1 OH 27 H H OCH 138-141 cl 23 cl ko ₂ h; h (c ₂ h ₅ : »8 51 - £> »3 ci ^z Hog 4-C1 OCH 186-189 29 - ^ L ^ -CN H H OK 52 - ^ ^CP 3 Cl ' Nog 4-C1 OH 230-252 30 so ₂ H OH • 53 - ^ ^CT 3 Cl from ₂ tt Cl OMa [ . 16700η ' ¹ ] 31 ^ Hio ₂ ch ₃ ci · ^ H H OH 54 - ^ Z ^ - ° ^cH j n ° ₂ H OH 32 - / '^ j -SCHj H you OH 55 - @ - ocf ₃ m ° ₂ H. OH 33 - £> ^CP 3 H H OH 201-205 cl MOg · 56 j ^ -oPj cl CN H OH 39 / ^ cf ₃ ON ^z H H OCH 129-131 35 2 - <J> ^CF 3 Cl ^ H OCH 3 · OH 57 '<2 ^ 3 cl N ° ₂ H N (CH 3) ₂ 174-177 36 -φ-CF Cl @ ko ₂ 3-OCH OH 165-192 .58 - £> 3 * Nog H N (CH 3) ₂ 155-158 37 O ^cp 3 'Cl ^z Nog 6-C1 OH 130-135 59 -PC ^p 3 KOG H HU - < 170-175 38 ^> ^C? 3 Cl ^ H0 ₂ P-6 OH 162-164 60 - £> ^CP 3 Cl H H OCH 100-104 39 ©> cf ₃ Cl ^ H 3-CH OH 156-159 61 Q-CFj H H OH 153-156 40 - @ - ^CP 3 Cl H 3-CH OCH 83-87 62 - @ ^ ^P 3 H 1! ONa [VJ " ₀ « 1680a "' ¹ : * 1 -p- ^cp 3 H 3-CH ONa C ^v cio * ^l ® ^{80 em} * ¹ l 63 -Qof ₃ from ₂ H OH 42 -gH ^P 3 ci- ^ Nog 3-CH OK 216-219 cl 64 ^ -CFj NO ₂ H OCH 85-92 * 3 . -0- ^cp 3 H 3-C1 OH 120-126 3r 49 Cl- - - ^ kf ₃ • Cl ^ N0 ₂ 3-C1 OH 209-211 65 - @ ^ 3 T> r NO ₂ H ' ONa C ^ sq * 1660c »* ¹ 45 - ^ ^P 3 WOMAN, 3-C1 OCH 140-143 ' 66 ^ ° ^P 3 Cl so ₂ 5-Cl OH 225-227 46 ©> - ^CP 3 Cl ^ H 3-F OH 67 7 ^ -ci cf ₃ H II OH 200-204

-5185902

Sorszóí g R ¹ R ² X Y Mp C ° C] Scfaz : 6n ^r1 R ² X Y Melting point [° C] 68 - <^ - Cl CP ₅ H H OCH 98-102 87 N0 ₂ H OH 69 -ξ ^ -Cl from ₂ H OH 88 - €> ^oh j N ° 2 H OH ^CP 3 cl 70 -Q »° a CP ₃ H H OH 184-187 E9 Cl 3 - ^CH 3 mo ₂ H OH 71 / ^ - ^N0 2 cp ₃ · H K OCH 142-146 90 ⁿ ° ₂ H OH 72 -Q-N ° 2 H H ONa C 1650 cm ^-1 ] 91 / □> H H OH - ^cf 3 Cl 92 O ^ci H H. ÖH 188-191 73 • ^ - ^CP 3 Cl H H . OH 93 zr ^CH 3 Á _S JI H H OH 74 - ^ ~ ^CP 3 F H H OH ' 94 , -7 ¹ H H OH 75 / ^ - ^Cp 3 P NO ₂ H OH 95 ° p H H OH 135-138 76 - <^ - ^cf 3 CH from ₂ H OH 96 ⁰ 'O · H H OCH 154-156 77 Q- ' N ° ₂ H OH 97 Λ- / '0 ₂ K ^^ H H OK CP, cl 78 - ^ - Cl H H OH 98 H H OH cl / ΓΆ ⁹⁹ H H OCH 150-152 79 N ° ₂ . H OH \ l 100 "-SHE H H OH 204-207 80 cl from ₃ H OH 101 H H ONa 8l F ! IQ ₂ H OH 102 '' ^c ^ nq ₂ 3-CH OCH 170-173 82 - ^ Z ^ -CN from ₂ H OH 103 p ₃ cQ Cl in the purified 3-OCH OCH 150-154 β3 -Qp CN from ₂ H OH 104 ° 2 ^Ν ^ Ξ> · H H ONa [V _Cr0 = lö ^ OcaT ¹ cl 105 Cl ^P 3 ^C ^ ' "° 2 5-Cl OH 223-227 84 T ^ ^CP 3 from ₂ H OH cl 106 "BOW" H H OCH 166-168 85 cl -0-C1 cl from ₂ yl OH 107 H H ONa Nc> o ^{158o <! N} ' ^1] cl 108 ^P 3 ^C ^> - H 6-Cl OCH n ^ ⁵ · 1.5858 86 from ₂ H OH cl

cl

185,902

1 2 Series R R X t Op .. t ° C] .Sorszám R ¹ R ² X Mp C ° C] 109 ^p jC - ^^ - ^H • 6-Cl OH LBL-185 127 N0 ₂ 8-OCH 175-178 110 H Ϊ1 6-Cl ONa [Vj.q'ISOOcb * ¹ ] 126 cl .no ₂ 8-CH 129-134 129 - £ X ^F 3 Cl H 8-CH 83-87 II. spreadsheet 130 j- ^CP 3 Cl Nog 5-C1 161-164 Serial number r ¹ R ² X M.p. 131 -Q ^CP 3 from ₂ 5- P 109-113 A- ^Cl - 111 H H cr 112 X> -C 1 N ° ₂ H 132 -O- ^CP 3 from ₂ 7-C1 138-141 cl cl 115 A- ^el Cl H II 133 - <Q- ^CP 3 H H 120-122 11¾ ^C1 Cl NO ₂ H 165-170 134 Cl - <Q- ^CP 3 N ° ₂ H 115 H H cl cl 135 H H 167-169 116 mo ₂ H M ^CP 3 117 b ^from 2 H 136 -Q-ol CPJ Nog H 118 Cl - £> ^cl Cl H H 137 + Q-no ₂ CPj H H 140-144 119 X N ° ₂ H 138 AX F H H 120 cl H H 141-163 139 - ^ OCF, = x / cl H H 121 ^c \ -Ö- ^CP 3 cr H H 160 - ^ ~ ^ -OCF ₃ Cl from ₂ H 122 Cl - ^ - ^CF 3 ^N0 2 K 141 CII from ₂ ' H 125 Cl O ^NO 2 H H, 193-195 142 AX CN from ₂ H 121 - ^ - ^H0 2 Cl H H 175-176 14}: -Qci Cl from ₂ H 125 cl Hog H int . Q * CN NO ₂ H 126 in the purified H Η 145-147 145 .-0- ^CT 3 Cl N0 ₂ H

-Ί185,902

Elaeis guineensis

Serial number r ¹

X Y

Melting point [° C]

1 ' THE/ from ₂ H 5 P NO ₂ H 1 * 8 H H 10 H9 M-H H H 167-170

Row song R ¹ R ² X Op. ('C) 150th 3-bromo-6- pyridyl H H 152-154 151st 4- (trifluoro ) -2-chloro- phenyl H 8-C1 120-128 152nd 4- (trifluoro methyl) -3-chloro- phenyl H 5-C1 150-153

Example 153

2- [3 '- (2-Chloro-4'-trifluoromethyl-phenoxy) -6'-nitro-phenyl] -4H-1,3-benzoxazin-4-one

In an analogous manner to Example 3, but 7 sr. anthranilic acid 37 sr. Reaction with 3- [2'-chloro-4 '- (trifluoromethyl) phenoxy] -6-nitrobenzoic acid chloride affords the title compound. 131-135 ° C.

The herbicides containing the active compounds of the formulas I and II can be used in a number of crop plants for controlling weeds. The amount of active ingredient used may vary from 0.1 to 15 kg, preferably from 0.2 to 3.0 kg, depending on the species and development of the weeds.

The herbicides according to the invention can be used, for example, in the following crop plants.

Allium cepa Pineapple comosus Arachis hypogaea Asparagus officinalis Beta vulgaris spp. altis- Avena sativa smooth Beta vulgar spp. escu- 50 Beta vulgaria spp. rapa lenta Brassica napus var. So- Brassica napus var. So- pus pobrassica Brassica napus var. RA Brassica rapa var. sIL 55 pa vestris Camellia sinensis Carthamus tinctorius Carya illinoinensis Citrus limon Citrus maxima Citrus reticulata Coffea arabica (Coffea canephora, Coffea libe- 60 Citrus sinensis rica) Cucumis job Cucumis sativus Cynodon dactylon Daucus carota 65

Fragaria vesca Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) Helianthus tuberosus Hordeum vulgare Ipomoea batatas Lactua sativa Linum usitatissimum

Malus spp.

Medicago sativa Musa spp.

Olea europaea Panieum miliaceum Phaseolus mungo Pennisetum glaucum

Picea abies Pinus spp.

Prunus avium Prunus dulcis Pyrus communis Ribes uva-crispa Saccharum officinarum Sesamum indicum Sorghum bicolor (s, vulgare)

Spinacia oleracea Trifolium pratense Vaccinium carymbosum

Vicia faba

Vitis vinifera ß herbicides for example

Glycine max Helianthus annuus Hevea brasiliensis Humulus lupulus Juglans regia Lens culinaris Lycopersiocon lycopersicum

Manihot esculenta Mentha piperita Nicotiana tabacum (N. rustica)

Oryza sativa Phaseolus lunatus Phaseolus vulgaris Petroseliním crispum spp. tuberosum Abies alba Pisum sativum Pmnus domestica Prunus persica Ribes sylvestre Ricinus communis Secale cereale

Solanum tuberosum Sorghum dochna Theobroma cacao

Triticum aestivum Vaccinium vitis-idaea Vigna sinensis (V. unguiculata)

Zea mays

The solutions according to the invention can be sprayed directly, as well as powders, suspensions - aqueous, oily or other suspensions containing a high active ingredient - or dispersions, emulsions, oily dispersions, pastes, dusts, sprays or granules, and their use in spraying, spraying, dusting, irrigation. The particular form of the herbicide is completely adapted to the intended use; in all cases, it should allow the homogeneous distribution of the active substance to be as uniform as possible.

Medium and high boiling petroleum fractions, such as kerosene or gas oil, as well as coal tar oil and vegetable or animal oils for the production of direct spray solutions and emulsions, pastes and oil dispersions; aliphatic, cyclic and aromatic hydrocarbons and their derivatives such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene, methanol, ethanol, propanes, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, a highly polar solvent such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water and the like. can be used.

Directly used aqueous preparations, emulsion concentrates, pastes or wetters

185,902 can be prepared by addition of water from sprayable powders, (spray powders), oil dispersions. For the preparation of emulsions, pastes or oil dispersions, the active compounds are optionally dissolved in an oil or solvent and are homogenized in water with the addition of a surfactant such as a wetting agent, tackifier, dispersant or emulsifier. Concentrates of the active ingredient and of the surfactant additive, such as wetting, tackifying, dispersing or emulsifying agents and optionally oils or solvents, may be prepared which may be diluted with water before use.

Alkali metal, alkaline earth metal and ammonium salts, naphthalenesulfonic acid, phenolsulfonic acid, alkylarylsulfonate, alkylsulfate, alkylsulfonate, dibutylnaphthalenesulfonic acid, alkali metal sulfide, sulphate, fatty alcohol sulphate, alkali metal and alkaline earth metal salts of fatty acids, salts of sulphated hexadecanols, heptadecanols and octadecanols, sulphated fatty alcohol glycol ether ethereal salts, sulphonated naphthalene and naphthalene derivatives, ethylene octylphenol ether, ethoxylated isooctyl phenol, octyl phenol and nonylphenol, alkyl phenol polyglycol ether, tributyl phenyl polyglycol ether, alkyl aryl polyether alcohol, isotridecyl alcohol, fatty alcohol ethylene oxide, ethoxylated ricin oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin, sulphite impurity and methyl cellulose, and the like. It can be used.

Powders, dusts and dusts may be prepared by mixing and / or grinding the active ingredient with a solid carrier.

Granules, such as coated, impregnated and homogeneous granules, may be prepared by binding the active ingredient to a solid carrier.

The solid carriers used in the agents of the present invention include mineral ground minerals such as silica gel, silica, silicate, kaolin, attapulgite, limestone, chalk, talc, bolus, loose, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide; ground plastic; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, as well as plant products such as cereal flour, cinnamon, wood and bone meal, cellulose powder and other known solid carriers are used.

The agents according to the invention contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight of the active ingredient.

. The following examples illustrate the composition and preparation of some representative agents of the invention. The active ingredient is identified by the serial number of the preparation example and by reference to Annexes I and II. .

Example I sr. Active ingredient 1 is mixed with 10 parts. N-methyl-pyrrolidone; 90% by weight of the active compound is obtained in the form of small droplets.

II. example sr. The active ingredient 2 is dissolved in 80 µl. xylene, 8-10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide in 10 parts by weight, 5 parts by weight. from the calcium salt of dodecylbenzenesulfonic acid, and a mixture of 40 mol of ethylene oxide and 1 mol of castor oil in 5 parts by weight. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

III. example sr. Active substance 37 is dissolved in 40 µl. of cyclohexanone, 30 sr. isobutanol, 20 parts by weight of an addition of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of an addition of 40 moles of ethylene oxide and 1 mole of castor oil. The solvent is 100,000 sr. poured into water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

ARC. example sr. Dissolve active ingredient 5 in 25 sr. of cyclohexanol, 65 sr. It was prepared from a petroleum fraction boiling in the range of 210-280 [deg.] C. and 40 parts by weight of ethylene oxide and 1 mol of castor oil in 10 parts by weight. The solution was diluted 100,000. poured into water and uniformly distributed to give an aqueous dispersion containing 0.02% by weight of active ingredient.

Example V sr. Active ingredient 4 is thoroughly mixed with 3 volumes. diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts lignin sulfonic acid sodium salt from a sulphite slurry and 60 parts powdered silica gel and grind in a hammer mill. The mixture was added at 20,000 sr. uniformly distributed in water to give a spray liquid containing 0.1% active ingredient.

VI. example sr. Active ingredient 20 is intimately mixed with 97 parts by weight. powdered kaolin. 3 sr. a powder containing the active ingredient is obtained.

185,902

VII. example sr. 96. The active ingredient is thoroughly mixed with 92 parts. powdered silica gel and sprayed on silica gel 8 sr. paraffin oil. Thus good tapadóképessé- ⁵ GU ingredient is obtained.

VIII. example sr. Active ingredient 11 is thoroughly mixed with 2 volumes. calcium salt of dodecylbenzenesulfonic acid, 8 sr. fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol, urea and formaldehyde condensate and 68 parts by weight. with paraffinic mineral oil. A stable, oily dispersion of ¹⁵ is obtained.

Agents having the formula N-benzoyl-antranilsavszármazékokat and anhidrovegyületeíket formula (II) (I), other herbicides and growth regulating agents active material ²⁰ may be mixed or herbicidal compositions according to the invention can also be used together with other herbicides and growth regulating agents. For example, the following structural groups may be incorporated into the agents of the present invention: diazines, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, bis-carbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, etc. These 3θ combinations are intended to increase the spectrum of action and also to produce a synergistic effect. Of course, the agents according to the invention may contain one or more active compounds of the general formula (I) or (II). 35

For example, the following active compounds may be mixed with the agents of the invention according to the needs of different applications:

5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-phenyl-3 (2H) -pyridazinone, 40

5-amino-4-chloro-2-cyclohexyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-cyclohexyl-3 (2H) -pyridazinone,

5-methylamino-4-chloro-2- [m- (trifluoromethyl) phenyl] 3 (2H) -pyridazinone, 45

5- (methylamino) -4-chloro-2- [m- (a, a, p, P-tetrafluoroethoxy) phenyl] -3 (2H) -pyridazinone,

5- (dimethylamino) -4-chloro-2-phenyl-3 (2H) -pyridazinone,

4.5-dimethoxy-2-phenyl-3 (2H) -pyridazinone, ₅₀

4.5-dimethoxy-2-cyclohexyl-3 (2H) -pyridazinone,

4,5-dimethoxy-2- [m- (trifluoromethyl) phenyl] -3 (2H) -pyridazinone,

5-Methoxy-4-chloro-2- [m- (trifluoromethyl) phenyl] 3 (2H) -pyridazinone, ₅₅

5-amino-4-bromo-2- [m-methyl-phenyl] -3 (2H) -pyridazinone,

3- (1-methylethyl) -1H-2,1,3-benzothiadiazine-4 (3H) on-2,2-dioxide and its salts,

3- (1-methylethyl) -8-chloro-1H-2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide and its salts,

3- (1-methylethyl) -8-fluoro-1H-2,1,3-benzothiadiazin4 (3H) -one-2,2-dioxide and its salts,

3- (1-methylethyl) -8-methyl-1H-2,1,3-benzothiadiazin4 (3H) -one-2,2-dioxide and its salts,

-methoxymethyl-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

-methoxymethyl-8-chloro-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

- methoxymethyl-8-fluoro-3- (1-methyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

cyano-8-chloro-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

cyano-8-fluoro-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

- cyano-8-methyl-3- (1-methylethyl) -2,3,3-benzothiadiazin-4 (3H) -one-2,2-dioxide,

attained by 3- (l-methylethyl) -2,1,3-benzotiadiazin4 (3H) -one-2,2-dioxide,

azidomethyl-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide;

3- (1-methylethyl) -1H-pyridino [3,2-e] -2,1,3-thiadiazin4-one-2,2-dioxide,

N- (l-ethyl-propyl) -2,6-dinitro-3,4-dimethyl-aniline,

N - (1-methylethyl) -N-ethyl-2,6-dinitro-4- (trifluoromethyl) aniline,

N- (n-propyl) -N- (3-chloroethyl) -2,6-dinitro-4- (trifluoromethyl) aniline,

N- (n-propyl) -N- (cyclopropylmethyl) -2,6-dinitro-4-trifluoromethylaniline,

N-bis (n-propyl) -2,6-dinitro-3-amino-4- (trifluoromethyl) aniline,

N-bis (n-propyl) -2,6-dinitro-4-methylaniline,

N-bis (n-propyl) -2,6-dinitro-4- (methylsulfonyl) aniline

N-bis (n-propyl) -2,6-dinitro-4- (aminosulfonyl) aniline, bis (p-chloroethyl) -2,6-dinitro-4-methylaniline,

N-ethyl-N- (2-methylallyl) -2,6-dinitro-4- (trifluoromethyl) aniline,

N-methyl-carbamic acid 3,4-dichlorobenzyl ester;

N-methyl-carbamic acid, 2,6-di (t-butyl) -4-methylphenyl ester,

N-phenyl-carbamic acid isopropyl ester,

N- (3-fluorophenyl) carbamic acid (3-methoxy-propyl-2) ester,

N- (3-chlorophenyl) -carbamic acid isopropyl ester, N- (3-chlorophenyl) -carbamic acid (butin-1-yl) -3-ester,

N- (3-chlorophenyl) carbamic acid (4-chloro-butyn-2-yl) ester,

N- (3,4-dichloro-phenyl) -carbamic acid methyl ester,

N- (4-amino-benzenesulfonyl) -karbamidsavmetil ester,

O- (N-phenylcarbamoyl) propanone oxime,

N-ethyl-2- (phenylcarbamoyl) -oxipropionsavamid,

3 '- (N-isopropylcarbamoyloxy) propionanilide, ethyl N- [3- (N'-phenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-methyl) -N'-phenylcarbamoyloxy) phenyl] carbamate, isopropyl N- [3- (N'-ethyl-N'-phenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- ( N'-3-methylphenylcarbamoyloxy) phenyl] carbamate, methyl N- (3 '(N'-4-fluorophenylcarbamoyloxy) phenyl] carbamate, methyl N- [3 - (N'-3-chloro-4-fluoro-phenyl-carbamoyloxy) phenyl] carbamate,

-101

185,902 ethyl N- [3- (N'-3-chloro-4-fluorophenylcarbamoyloxy) phenyl] carbamate, ethyl N- [3- (N'-3,4-difluorophenyl) carbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-3,4-difluorophenylcarbamoyloxy) phenyl] carbamate,

N-3- (4-fluoro-phenoxy-carbonyl-amino) -fenilkarbamidsav methyl ester,

N-3- (2-methyl-phenoxy-carbonyl-amino) -fenilkarbamidsav ethyl ester,

N-3- (4-fluoro-phenoxy-carbonyl-amino) -feniltiokarbamidsav methyl ester,

N-3- (2,4,5-trimethyl-phenoxy-carbonylamino) -feniltiokarbamidsav methyl ester,

N-3- (phenoxy-carbonylamino) phenyl-thiocarbamic acid methyl ester,

Ν, Ν-diethyl-thiocarbamic acid p-chlorobenzyl ester,

N, N-di-n-propyl-thiocarbamic acid ethyl ester,

N, N-di-n-propyl dithiocarbamic acid (n-propyl) ester,

N, N-di-isopropyl-dithiocarbamic acid (2,3-dichloroallyl) ester,

N, N-di-isopropyl-dithiocarbamic acid (2,3,3-trichloroallyl) ester,

N, N-diisopropyl-thiocarbamic acid 3-methyl-5isoxazolyl methyl ester,

N, N-diisopropyl-thiocarbamic acid 3-ethyl-5-isoxazolyl-methyl ester,

N, N-di-sec-butyl-thiocarbamic acid ethyl ester,

N, N-di-sec-butyl-thiocarbamic acid benzyl ester,

N-ethyl-N-cyclohexyl thiocarbamic acid ethyl ester,

N-ethyl-N-bicyclo- [2,2, l] heptyl tiokarbamidsavetil ester,

S- (2,3-dichloroallyl) - (2,2,4-trimethylazetidine) -1-carbothiolate,

S- (2,3,3-trichloro-allyl) - (2,2,4-trimethyl-azetidin) -lkarbotiolát,

S-ethylhexahydro-1H-azepine-1-carbothiolate, S-benzyl-3-methylhexahydro-1H-azepine-1-carbothiolate,

S-benzyl-2,3-dimethylhexahydro-1H-azepine-1 carbothiolate,

S-ethyl-3-methylhexahydro-1H-azepine-1-carbothiolate,

N-ethyl-N-n-butyl-n-propyl tiolkarbamidsav,

N, N-dimethyl-ditiokarbamidsav- (2-chloro-allyl) ester,

Sodium salt of N-methyl dithiocarbamic acid, sodium salt of trichloroacetic acid, sodium salt of α-α, -dichloropropionic acid, sodium salt of α, α-dichlorobutyric acid, α, α, β, β-tetrafluoropropionic acid, sodium methyl-α-dichloropropionic acid, methyl methyl α-chloro-4- (4-chlorophenyl) propionic acid, methyl methyl dichloro-4-phenylpropionic acid, benzamidooxyacetic acid .

2.3.5-Triiodobenzoic acid, its salts, esters and amides,

2.3.6-Trichlorobenzoic acid, its salts, esters and amides,

2.3.5.6- tetrachlorobenzoic acid, its salts, esters and amides,

2-methoxy-3,6-dichlorobenzoic acid, its salts, esters and amides,

2-methoxy-3,5,6-trichlorobenzoic acid, its salts, esters and amides,

3-amino-2,5,6-trichlorobenzoic acid, its salts, esters, amides,

O, S-dimethyl-tetrachlorothiophthalate, dimethyl-2,3,5,6-tetrachloro-terephthalate, disodium 3,6-endoxo-hexahydrophthalate,

4-amino-3,5,6-trichloro-picolinic acid and its salts,

5-Cyano-3- (N-methyl-N-phenyl) amino-ethyl acrylate,

2- [4- (4'-chlorophenoxy) -phenoxy] -propionic acid isobutyl ester,

2- [4- (2 ', 4'-dichlorophenoxy) phenoxy] propionic acid methyl ester,

2- [4- (4 '- / trifluoromethyl / -phenoxy) -phenoxy-propionic acid methyl ester,

2- [4- (2 ^/ chloro-4 '- (trifluoromethyl) phenoxy) phenoxy] propionic acid sodium salt prc,

2- [4- (3 ', 5'-dichloro-2-pyridyl) phenoxy] propionic acid,

2- (N-benzoyl-3,4-dichloro-phenylamino) -propionic acid ethyl ester,

2- (N-benzoyl-3-chloro-4-fluoro-phenylamino) -propionic acid methyl ester,

2- (N-benzoyl-3-chloro-4-fluoro-phenylamino) -propionic acid isopropyl ester,

2-chloro-4- (ethylamino) -6- (isopropylamino) -1,3,5triazin,

2-chloro-4- (ethylamino) -6- (amino-2'-propionitrile) 1.3.5-triazine,

2-chloro-4- (ethylamino) -6- (2-methoxy-propylamino) -l, 3,5-triazine,

2-chloro-4- (ethylamino) -6- (butin-1-yl-2-amino) 1,3.5-triazine,

2-chloro-4,6-bis (ethylamino) -1,3,5-triazine, 2-chloro-4,6-bis (isopropylamino) -1,3,5-triazine,

2-chloro-4- (isopropylamino) -6- (cyclopropylamino) -1,3,5-triazine,

2-azido-4- (methylamino) -6- (isopropylamino) -1,3,5-triazine,

2- (methylthio) -4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine,

2- (methylthio) -4- (ethylamino) -6- (tert-butylamino) -1,3,5-triazine,

2- (methylthio) -4,6-bis (ethylamino) -1,3,5-triazine, 2- (methylthio) -4,6-bis (isopropylamino) -1,3, 5triazin,

2-methoxy-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine,

2-methoxy-4,6-bis (ethylamino) -1,3,5-triazine, 2-methoxy-4,6-bis (isopropylamino) -1,3,5-triazine,

4-amino-6- (tert-butyl) -3- (methylthio) -4,5-dihydro-l, 2,4-triazin-5-one,

4-amino-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one,

4- (isobutylidene) -6- (tert-butyl) -3- (methylthio) -4,5-dihydro-1,2,4-triazin-5-one,

-methyl-3-cyclohexyl-6- (dimethylamino) -13,5-triazine 2,4-dione,

3- (tert-butyl) -5-chloro-6-methyluracil, 3- (tert-butyl) -5-bromo-6-methyluracil, 3-isopropyl-5-bromo-6-methyluracil, 3- (sec-butyl) -5-bromo-6-methyluracil, 3- (2-tetrahydropyranyl) -5-chloro-6-methyluracil, 3- (2-tetrahydropyranyl) -5, 6-trimethylene-uracil, 3-cyclohexyl-5,6-trimethylene-uracil,

-111

185,902

2-methyl-4- (3 '- / trifluoromethyl / phenyl) -tetrahidro1,2,4-oxadiazine-3,5-dione,

2-methyl-4- (4'-fluorophenyl) -tetrahydro-1,2,4-oxadiazine-3,5-dione,

3-amino-1,2,4-triazole,

- (allyloxy) -1- (4-bromophenyl) -2- (1 ', 2', 4'-triazolyl ') ethane and its salts, [1- (1,2,4-triazolyl) - 1 ')] - [1- (4'-chlorophenoxy)] - 3,3-dimethylbutan-2-one,

N, N-diallyl chloroacetamide,

N-isopropyl-2-chloroacetanilide,

N- (l-butyn-3-yl) -2-chloro-acetanilide,

2-methyl-6-ethyl-N- (propargyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (ethoxymethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (2-methoxy-1-methylethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (isopropoxycarbonyl-ethyl) -2-chloro-acetanilide

2-methyl-6-ethyl-N- (4-methoxypyrazol-1-ylmethyl) -2-chloroacetanilide,

2-methyl-6-ethyl-N- (pyrazol-1-ylmethyl) -2-chloroacetanilide,

2.6-dimethyl-N- (pyrazon-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (4-methylpyrazol-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (1,2,4-triazol-1-ylmethyl) -2-chloroacetanilide,

2.6-dimethyl-N- (3,5-dimethylpyrazol-1-ylmethyl) -2-chloroacetanilide,

2,6-dimethyl-N- (1,3-dioxolan-2-ylmethyl) -2-chloroacetanilide,

2.6-dimethyl-N- (2-methoxyethyl) -2-chloroacetanilide,

2.6-dimethyl-N- (isobutoxymethyl) -2-chloroacetanilide,

2.6-diethyl-N- (methoxymethyl) -2-chloroacetanilide,

2.6-diethyl-N- (n-butoxymethyl) -2-chloroacetanilide,

2.6-diethyl-N- (ethoxycarbonylmethyl) -2-chloroacetanilide, _y

2,3,6-trimethyl-N- (pyrazol-l-yl) -2-chloroacetanilide,

2,3-dimethyl-N- (isopropyl) -2-chloroacetanilide,

2- (2-methyl) -4-chloro-phenoxy-N-methoxy-acetamide,

2- (a-naphthoxy) -N, N-diethyl-propionamide

2,2-diphenyl-N, N-dimethylacetamide, α- (3,4,5-tribromopyrazol-1-yl) -N, N-dimethylpropionamide,

N- (l, l-dimethyl-propynyl) -3,5-dichlorobenzamide,

N-1-naphthylphthalamic acid, propionic acid 3,4-dichloroanilide, cyclopropanecarboxylic acid 3,4-dichloroanilide, methacrylic acid 3,4-dichloroanilide,

2-methyl-pentanoic acid 3,4-dichloro-anilide,

N-2,4-dimethyl-5- (trifluoromethyl-sulfonyl-amino) phenyl-acetamide,

N-4-methyl-5- (trifluoromethyl) sulfonyl-aminophenyl-acetamide,

2- (propionylamino) -4-methyl-5-chloromethyl-thiazole;

0- (methylsulfonyl) glycolic acid-N- (ethoxymethyl) -2,6-dimethyl-anilide,

0- (methylamino-sulfonyl) -N-isopropyl-glycolic anilide,

O- (isopropylaminosulfonyl) glycolic acid N-butyn-1-yl-3-anilide,

O- (methyl-aminosulfonyl) hexametiIénamid-glycolic acid,

2.6-dichlorothiobenzamide,

2.6-dichlorobenzonitrile,

3.5-dibromo-4-hydroxybenzonitrile and its salts,

3.5-Diiodo-4-hydroxybenzonitrile and its salts,

3,5-dibromo-4-hydroxy-O- (2,4-dinitrophenyl) benzaldoxime and its salts,

3.5-dibromo-4-hydroxy-O- (2-cyano-4-nitrophenyl) benzaldoxime and its salts, pentachlorophenyl sodium salt,

2.4-dichlorophenyl-4'-nitrophenyl ether,

2.4.6-trichlorophenyl-4'-nitrophenyl ether, 2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether, 2-chloro-4- (trifluoromethyl) - phenyl 4'-nitrophenyl ether, 2,4'-dinitro-4- (trifluoromethyl) diphenyl ether,

2.4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether, 2-chloro-4- (trifluoromethyl) phenyl-3'-ethoxy-4'-nitrophenyl ether,

2-chloro-4- (trifluoromethyl) phenyl-3'-carboxy-4'-nitrophenyl ether and its salts,

2-chloro-4- (trifluoromethyl) phenyl-3'-ethoxy-karbonil4'-nitrophenyl ether,

2,4-dichloro-phenyl-3 '- (methoxycarbonyl) -4'-nitrophenyl ether,

2- (3,4-dichlorophenyl) -4-methyl-1,2,4-oxadiazolidin3,5-dione,

2- (3- tert -butylcarbamoyloxy-phenyl) -4-methyl-1,2,4-oxadiazolidine-3,5-dione, 2- (3-isopropylcarbamoyloxy-phenyl) -4- methyl 1,2,4-oxadiazolidine-3,5-dione,

2-phenyl-3,1-benzoxazin-4, (4-bromo-phenyl) -3,4,5,9,10-pentaaza-tetracyclo [5,4.1.0 ²⁶ 0 ^s] dodeca-3,9- diene

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-sulfonate benzofuranilmetán,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-amino-benzofuranildimetil sulfate

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl (N-methyl-N-acetyl) -aminoszulfonát,

3,4-dichloro-1,2-benzisothiazole, N- (4-chlorophenylallyl) succinic acid imide, 2-methyl-4,6-dinitrophenol, its salts, esters, 2- (sec-butyl) -4, 6-Dinitrophenol, salts, esters, 2- (sec-butyl) -4,6-dinitrophenol acetate, 2- (tert-butyl) -4,6-dinitrophenol acetate, 2- (tert-butyl) butyl) -4,6-dinitrophenol, salts, 2- (tert-butyl) -5-methyl-4,6-dinitrophenol, salts, 2- (tert-butyl) -5-methyl-4, 6-dinitrophenol acetate, 2-secamyl-4,6-dinitrophenol, its salts and esters, 1- (a, a-dimethylbenzyl) -3- (4-methylphenyl) urea, l-phenyl-3- (2-methylcyclohexyl) -urea,

1-phenyl-1-benzoyl-3,3-dimethylurea,

- (4-chlorophenyl) -1-benzoyl-3,3-dimethylurea, 1- (4-chlorophenyl) * 3,3-dimethylurea, 1- (4-chlorophenyl) -3 dimethyl-3-butyn-l-3-yl-urea,

1- (3,4-dichlorophenyl) -3,3-dimethylurea, 1- (3,4-dichlorophenyl) -1-benzoyl-3,3-dimethylurea, 1- (3,4) dichlorophenyl) -3-methyl-3-n-butylurea, 1- (4-isopropylphenyl) -3,3-dimethylurea,

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185 902 1- (3-Trifluoromethylphenyl) -3,3-dimethylurea,

- (α, α, p, p-tetrafluoroethoxyphenyl) -3,3-dimethylurea,

- (3-tert-Butylcarbamoyloxy-phenyl) -3,3-dimethyl-urea, 1- (3-chloro-4-methyl-phenyl) -3,3-dimethyl-urea, 1- (3-chloro-4-) methoxyphenyl) -3,3-dimethylurea, 1- (3,5-dichloro-4-methoxyphenyl) -3,3-dimethylurea, 1- [4- (4'-chlorophenoxy) -phenyl] -3,3-dimethylurea, 1- [4- (4'-methoxyphenoxy) phenyl] -3,3-dimethylurea, 1-cyclooctyl-3,3-dimethylurea, - (hexahydro-4,7-methane-indan-5-yl) -3,3-dimethylurea,

1- [1- or 2- (3a, 4,5,7,7a-hexahydro) -4,7-methanoindanyl] -3,3-dimethylurea, 1- (4-fluorophenyl) -3-carboxy methoxy-3-methylurea,

phenyl-3-methyl-3-methoxy-urea, 1- (4-chlorophenyl) -3-methyl-3-methoxy-urea, 1- (4-bromophenyl) -3-methyl-3-methoxy urea, 1- (3,4-dichloro-phenyl) -3-methyl-3-methoxy-urea, 1- (3-chloro-4-bromo-phenyl) -3-methyl-3-methoxy-urea, - (3-Chloro-4-isopropyl-phenyl) -3-methyl-3-methoxy-urea, 1- (3-chloro-4-methoxy-phenyl) -3-methyl-3-methoxy-urea, 1- (3-tert-butyl) butylphenyl) -3-methyl-3-methoxyurea, 1- (2-benzothiazolyl) -1,3-dimethylurea, 1- (2-benzothiazolyl) -3-methylurea,

- (5- (trifluoromethyl) -1,3,4-thiadiazolyl) -1,3-dimethylurea, 1- (4- (benzyloxy) phenyl) -3-methyl-3-methoxy- urea, imidazolidin-2-one-1-carboxylic acid isobutylamide,

1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate, 1,2,4-trimethyl-3,5-diphenylpyrazolium methyl sulfate,

1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulfate, 1,3-dimethyl-4- (3,4-dichlorobenzoyl) -5-1- (4-methylphenylsulfonyl) oxy] - pyrazole,

2,3,5-trichloro-4-pyridinol,

1-methyl-3-phenyl-5- (3 '- (trifluoromethyl) phenyl) pyridone-4,

1-methyl-4-phenylpyridinium chloride,

1,1-dimethylpyridinium chloride, 3-phenyl-4-hydroxy-6-chloropyridazine,

1,1'-dimethyl-4,4'-dipyridylium di- (methylsulphate),

1,1'-di- (3,5-dimethylmorpholylcarbonylmethyl) 4,4'-di-pyridylium dichloride,

1,1'-ethylene-2,2'-dipyridilium dibromide,

3- [l- (N-ethoxycarbonyl-amino) propylidene] -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione,

3- [l- (N-allyl-oxy) propylidene] -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione,

2- [1- (N-Allyloxyamino) propylidene] -5,5-dimethylcyclohexane-1,3-dione and its salts,

2- [1- (N-Allyloxyamino) butylidene] -5,5-dimethylcyclohexane-1,3-dione and its salts,

2- [1- (N-Allyloxyamino) butylidene] -5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione and its salts,

2-chlorophenoxyacetic acid, its salts, esters, amides,

4-Chlorophenoxyacetic acid, its salts, esters, amides,

2,4-dichlorophenoxyacetic acid, its salts, esters, amides,

2.4.5-Trichlorophenoxyacetic acid, its salts, esters, amides

2-methyl-4-chlorophenoxyacetic acid, its salts, esters, amides,

3.5.6-trichloro-2-pyridinyloxyacetic acid, its salts, esters, amides, methyl c-naphthoxyacetic acid,

2- (2-methylphenoxy) propionic acid, its salts, esters, amides,

2- (4-chlorophenoxy) propionic acid, its salts, esters, amides,

2- (2,4-Dichlorophenoxy) -propionic acid, its salts, esters, amides,

2- (2,4,5-trichlorophenoxy) propionic acid, its salts, esters, amides,

2- (2-methyl-4-chlorophenoxy) -propionic acid, salts, esters, amides, (2,4-dichlorophenoxy) butyric acid, salts, esters, amides, (2-methyl-4-chlorophenoxy) ) -butyric acid, its salts, esters, amides, cyclohexyl-3- (2,4-dichlorophenoxy) acrylate,

9-hydroxy-fluorenecarboxylic acid 9, its salts, esters,

2.3.6-Trichlorophenylacetic acid, its salts, esters,

4-Chloro-2-oxo-benzothiazolin-3-yl-acetic acid, its salts, esters of gibelleric acid and its salts, disodium methyl-arsonate, monosodium-methyl-arsonate, N-phosphonomethylglycine and its salts, N, N- bis (phosphonomethyl) glycine and its salts, 2-chloroethane phosphonic acid 2-chloroethyl ester, ammonium ethylcarbamoyl phosphonate, di-n-butyl-1-n-butylaminocyclohexyl -phosphonate, trithio-butylphosphite,

O, O-diisopropyl-5- (2-benzosulfonylaminoethyl) -phosphorothionate,

2,3-dihydro-5,6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide,

5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2,

4,5-dichloro-2-trifluoromethyl-benzimidazole and its salts,

1.2.3.6-Tetrahydropyridazine-3,6-dione and its salts, succinic mono-N-dimethylhydrazide and its salts, (2-chloroethyl) trimethylammonium chloride, (2-methyl-4-phenyl) sulfonyl) trifluoro-methane-sulfonanilide,

1,1-dimethyl-4,6-diisopropyl-5-indanylethyl ketone,

2- [1- (2,5-Dimethyl-phenyl) -ethylsulfonyl] -pyridine Noxide, Sodium Chlorate, Ammonium Rhodanide, Calcium Cyanide.

Further herbicides, such as pesticides, fungicides and bactericides, may be combined with the herbicides of the present invention or combinations thereof with other herbicides. The herbicides of the invention may also be mixed with mineral saline solutions; they are suitable for the elimination of trace element deficiencies and for stimulating metabolic processes.

-13185902

Explanation of the effect of herbicides of the invention may be facilitated by moistening and adhesion promoting additives as well as non-phytotoxic oils and oil concentrates by adding ₅

The effect of the herbicides according to the invention on crop plants and weeds was investigated in greenhouse experiments.

300 ml plastic _1θ flower pots filled with clayey sand containing 1.5% humus were used as _breeding pots. Seeds of the experimental plants listed below were planted in the soil.

Cyperus esculentus was planted from germinated bulbs.

For pre-emergence treatment, the soil surface was treated with the test substance immediately after planting. II-V. The preparation of any of Examples 1 to 4 was suspended or emulsified in water and sprayed with a finely divided atomiser. After treatment with the agent, the dishes were lightly watered to induce germination and development of the seeds and to activate the active ingredient. The dishes were then covered with a transparent plastic lid. The purpose of the cover was to uniformly germinate the seeds of the plants, unless this was affected by the agent.

For post-emergence treatment, the plants were allowed to grow to a height of 3-10 cm according to their nature and then treated. Some plants were germinated directly in the culture vessel, others were pre-germinated in a flask and transplanted into experimental vessels only a few days before treatment. These plants were not covered.

The experimental vessels were kept in a greenhouse and the warm-loving species were stored at 25-40 ° C and the temperate climate lovers were stored at 15-30 ° C. The experimental period was 2-4 weeks. During this time, the plants were nurtured and monitored for development. The results were evaluated on a scale from 0 to 100. 0 means that the plants are not damaged and have developed properly; 100 means that the seed has not hatched or at least the above-ground parts of the plant are completely dead.

The results obtained are shown in Sections III-XIV. Table 1. The results prove that the herbicides according to the invention have selective herbicidal activity. Some agents specifically control some broadleaf weeds, others simultaneously control broadleaf and herbaceous weeds; the herbicide also extends to Cyperaceae. The agents of the invention may be applied before and after emergence; post-emergence application is preferred. In one particular application, the agents of the present invention are sprayed in the form of a spray liquid so that the spray juice does not get onto the leaves of the more sensitive crop plants, only to the soil below and to the weeds growing there ("post-directed" or "Iay-by" mode).

The herbicides according to the invention were tested on the following plants;

Abutilon theophrasti Arachis hypogaea Bromus spp.

Centaurea cyanus Chrysanthemum segetum

Amaranthus retroflexus Beta vulgaris Bidens pilosa Chenopodium album Cyperus esculentus

Cyperus ferax Digitaria sanguinalis Glycine max Ipomoea spp.

Oryza sativa Poíygonum persicaria Setaria spp.

Sinapis alba Triticum aestivum Acanthospermum hispidum

Avena fatua Hordeum vuigare Mercurialis annuua

Datura stramonium Euphorbia geniculata Helianthus annuus Nicandra physaloides Pisum sativum Sesbania exaltata Asclepias syriaca Solanum nigrum Zea mays Asclepias spp.

Centaurea cyanus Lamium amplexicaule Viola spp.

Table IIL

Selective herbicide against Chenopodium album containing active ingredient No 20 in sugar beet and other crops (post-emergence treatment in a greenhouse)

Damage% 0.4 kg / ha

Experimental plant 1.0 agent Beta vulgar 0 0 Helianthus annuus 0 0 Pisum sativum 0 0 Chenopodium album 99 99

ARC. spreadsheet

The selective herbicidal activity of active ingredient No. 127 against Amaranthus retroflexus in sugar beet and wheat is the product containing 2- (3-trifluoromethyl-phenyl) -4H-3,1-benzoxazin-4-one (U.S. Pat. No. 3,914,121). patent) in a greenhouse (post-emergence treatment)

Experimental plant Damage,% 0.5 kg / ha 127. active - 0.5 kg / ha Nyagan known effect. Beta vulgar 10 95 Triticum aestivum 10 0 Amaranthus retroflexus 90 16

Table V.

Agent No. 4 contains Cyperus esculentus and Setaria spp. herbicide in various crops (post-emergence treatment in greenhouses)

Experimental plant % Damage 0.4 kg / ha of active substance Arachis hypogaea 0 Glycine max 12 Oryza sativa 10 Pisum sativum 0 Zea mays 10 Cyperus esculentus 80 Setaria spp. 80

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VI. spreadsheet

Herbicide against Digitaria sanguinalis in soya and rice (post-emergence treatment in a greenhouse)

Experimental plant % Damage 0.5 kg / ha of active substance Glycine max 0 Oryza sativa 0 Digitaria sanguinalis 80

Table X.

Herbicidal Activity of Agent No. 5 Compared to Agent Containing 2-Phenyl-4H-3,1-Benzoxazin-4-One (German Patent No. 1,191,171) (Post-emergence treatment in a greenhouse)

VII. spreadsheet

Cyperus spp. in peanuts and rice with agent 11 (post-emergence treatment in a greenhouse)

% Damage Experimental plant 0.5 kg / ha 0.25 kg / ha agent Arachis hypogaea 0 Oryza sativa 10 0 Cyperus ferax 100 100

% Damage

Experimental plant 0.4 kg / ha 5. active ingredient 4.0 kg / ha of known active substance Arachis hypogaea 5 0 Abutilon theophrasti 98 10 Asclepias syriaca 90 0 Bidens pilosa 95 20 Datura stramonium 85 10 Digitaria sanguinalis 90 - Euphorbia geniculata 98 20 Nicandra physaloides 100 98 Setaria spp. 80 0 Sinapis alba 95 95 Solanum nigrum 100 65

VHI. spreadsheet

Selective action of broadleaf weeds on peanuts (post-emergence treatment in greenhouses)

XI. spreadsheet

Herbicidal Effects of the Invention on Pre-emergence and Post-emergence (Greenhouse Test)

Experimental plant % Damage 0.4 kg / ha of active substance Arachis hypogaea 0 Euphorbia geniculata 85 Solanum nigrum 80

Serial number of the active substance

Application rate kg / ha

Plants tested and their damage,%

Before hatching

Sinapis alba

After hatching

Ipomoea cyanus ^S PP '

IX. spreadsheet

Herbicidal activity of agent 2 containing active ingredient 2- (3-trifluoromethyl-phenyl) -4H-3,1-benzoxazin-4-one in various crop plants (U.S. Pat. No. 3,914,121) compared (post-emergence treatment in a greenhouse)

42nd 3.0 100 90 - 36th 3.0 100 90 90 52nd 3.0 90 90 - 102nd 3.0 100 100 100 53rd 3.0 90 100 - 132nd 3.0 - 90 80 114th 3.0 100 100 100 128th 3.0 90 100 100 103rd 3.0 100 100 100

Experimental plant % Damage 0.25 kg / ha of active ingredient 2 0.25 kg / ha of known active substance Arachis hypogaea 10 0 Glycine max 10 22 Oryza sativa 2 0 Pisum sativum 10 2 Abutilon theophrasti 100 10 Bromus spp. 80 0 Crysanthemum sege- 100 82 Tum Cyperus ferax 99 30 Digitaria sanguinalis 90 0 Polygonum persicaria 98 60 Sesbania exaltata 92 90 Setaria spp. 90 0

XII. spreadsheet

Selective herbicidal activity of active substance No 120 in various cereals (post-emergence treatment in a greenhouse)

% Damage 1.0 kg / ha 2.0 kg / ha active ingredient

Experimental plants

Hordeum vulgare 0 0 Oryza sativa 10 10 Triticum aestivum 0 0 Acanthospermum hispidum 100 100 Asclepias spp. 98 100

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% Damage 1.0 kg / ha 2.0 kg / ha active ingredient

Experimental plants

Chenopodium album Chrysanthemum sege- IOO 100 100 100 Tum Euphorbia geniculata 100 100 Lamium amplexicaule 80 80 Nicandra physaloides 100 100 Solanum nigrum 75 75 Sinapis alba 80 100 XIII. spreadsheet Selective herbicide effect of active ingredient number 40 (post-emergence treatment increased house-counter) Experimental plants % Damage 0.5 kg / ha of active substance Triticum aestivum 5 Amaranthus retrofle- 100 Taxus Avena fatua 80 Ipomoea spp. 95

XIV. spreadsheet

Effect of broadleaf weed control on active substance 43 in cereals (post-emergence treatment in a greenhouse)

% Damage

Experimental plants 1.0 kg / ha 2.0 kg / ha agent Triticum aestivum 5 5 Centaurea cyanus 98 98 Ipomoea spp. 100 100 Mercurialis annuua 95 95 Sinapis alba 100 100 Viola spp. 80 90

= no damage 100 = total destruction

Claims (2)

CLAIMS 1. An herbicide comprising from 0.1 to 95% by weight of an N-benzoyl anthranilic acid derivative of the formula I or an anhydro compound of the formula II, wherein R ¹ is a phenyl group wherein R ^{3 is} halogen and R ^{4 is} halogen or C 1-4 haloalkyl; R ^{2 is} hydrogen or nitro; X is hydrogen or halogen, (C1-C4) alkyl or (C1-C4) alkoxy; Y is -OR ⁶ wherein R ^{6 is} hydrogen or alkali metal or C 1-4 alkyl is a solid or liquid carrier or diluent, preferably natural or artificial mineral powder, aliphatic, aromatic or cyclic hydrocarbon, petroleum fraction, and surfactant an additive, preferably an ionic or non-ionic dispersing, emulsifying or wetting agent. 2. Process for the preparation of N-benzoylanthranilic acid derivatives of the formula I and their anhydro compounds of the formula II - in the formulas ^R1 is (a) or (b) a phenyl group of the formula; ??? in these groups one of R ³ and R ⁴ is halogen, nitro or C 1 -C 4 haloalkyl and the other is hydrogen or halogen; and ^R1 6-chloro-3-pyridazinyl, 3-bromo-6-piridiI25 ^va w 3-nitro-6-pyridyl; R ^{2 is} hydrogen or nitro; X is hydrogen, halogen, C 1-4 alkyl or C 1-4 alkoxy, and ³⁰ Y ^R7-OR6 or-N </ ^ 8 radicals; in these groups R R is hydrogen, an alkali metal cation or a C 1-4 alkyl group, R ^{7 is a} hydrogen atom or a C 1-4 C 35 alkyl group and R ^{8 is a C} 1 M alkyl group, a) (I) Compounds of formula (III) is an anthranilic acid derivative of formula ₄₀ of the formula wherein X and Y are as defined above - essentially stoichiometric amounts of (IV), substituted benzoyl halide of the general formula: - wherein R ¹ and R ² or Hal is a halogen atom, or _{4g of the} anthranilic acid derivative of formula (II), wherein X is at least twice the molar excess of benzoyl halide of formula (IV) wherein R ¹ and R ^{2 are} as defined above and Hal is halogen, or c) cyclization of the N-benzoyl anthranilic acid derivative of formula I to the anhydro compound of formula II, wherein the symbols are as defined above, optionally a compound of formula I wherein R @ 3 is hydrogen; To a compound of formula (I) wherein R R is an alkali metal cation.